Dyeing nickel chelate modified polyolefin with azomethine dyes



United States Patent ABSTRACT OF THE DISCLOSURE Shaped polyolefines which contain organic nickel chelate complexes as dye acceptors are dyed or printed by contacting shaped articles of such polyolefine material with fine dispersions, either in the form of solution or fine suspensions of certain metallizable azo or azomethine dyestuffs which are capable of taking part in metal complex formation.

The present invention concerns a process for the dyeing and printing of shaped goods made from polyolefines and more particularly from polypropylene or polyethylene material, as well as an industrial product, the shaped polyolefine goods colored or printed according to this process.

To the best of our knowledge, no fully satisfactory dyeing process for previously shaped polyolefine articles, in particular polyethylene and polypropylene fibers was hitherto known; up to the present, dyeings attained by subjecting such previously formed material to a dyeing or printing process were of weak color depth and only of mediocre fastness to light.

It is, therefore, an object of our invention to provide shaped, colored olefine, and particularly polypropylene or polyethylene articles of deep shades and good fastness to light.

It has now surprisingly been found that shaped articles of polyolefine material of strong and light-fast shades are obtained by dyeing or printing such articles, the polyolefine of which contains organic nickel chelate complexes as dye acceptors, with fine dispersions, either in the form of solutions or fine suspensions of certain metallizable azo or azomethine dyestuffs defined below which are free from salt-forming, water-solubilizing groups, or containing only such salt-forming groups as defined below, which are capable of taking part in metal complex formation.

It is thus possible to attain the above-stated object as wel as others that will become apparent as the description of the invention proceeds. The resulting dyed and printed polyolefine goods are distinguished particularly by a lightfastness which is due, on the other hand to the good lightfastness properties of the resulting dye component in the colored material and, on the other hand, to the fact that the organic nickel chelate complexes have the double function of acting as dye acceptors and as light stabilizers, the combined effect being an excellent light-fastness of the dyed polyolefine article.

.The term organic nickel chelate complexes is used herein to describe polydentate organic chelating agents capable of acting as dye acceptors which preferably contain several oxygen atoms and in certain cases, in addition, sulfur or nitrogen atoms as donor atoms.

The starting polyolefine material which is dyed according to the invention contains preferably nickel chelate complexes of the aromatic series, preferably of :alkylated o,o'-dihydroxydiphenyl sulfides, each of the alkyl radicals advantageously containing about 4 to 12 carbon atoms. Polyolefine, which contains the nickel complex of 2,2'-dihydroxy-5,5'-diisooctyldiphenyl sulfide is particularly suitable for the dyeing process according to the inven- 3,399,027 Patented Aug. 27, 1968 tion because remarkable deep dyeings can be attained therewith. Other polyolefines containing a nickel chelate complex which are suitable for use according to the invention, are those containing nickel .acetylacetonate, nickel glycinate, 8-hydroxy-quinoline nickel complex, o-dihydroxybenzene nickel complex, o-hydroxy benzophenone nickel complex, salicylaldehyde nickel complex radicals; Ni-ethylene diamine tetraacetate can be used as second choice only, with less improvement in fastness of the dyeings. The foregoing other chelate complexes are preferred.

Primarily, polypropylene e.g. isotactic polypropylene, is used as polyolefine but also polyethylene as well as mixed polymers of these two olefines containing the abovedefined nickel chelates, can be dyed or printed according to the invention.

In addition to the nickel chelate complexes as defined, these polyolefines advantageously contain other additives such as antioxidants, additional light stabilizers, delustering agents, etc. The polyolefine material can 'be used in any form desired, eg as foils, granulates, and the like disperse dyes, but, preferably, as fibers. Advantageously, the content of nickel is about 0.1 to not more than 2% and preferably 0.1 to 1.2% of the weight of the material to be dyed; lower contents than 0.1% have a disadvantageous effect on the fastness properties of the resulting dyeings or prints.

The following classes of azo and azomethine dyestuffs are suitable for the dyeing and printing of the abovedescribed polyolefine materials in the process according to the invention.

1) Monoaz'o dyestuffs of the benzene-azobenzene and the benzene-azo-naphthalene series wherein one benzene nucleus must be substituted in o-position to the azo bridge by a hydroxy or COOH group, while the other benzene nucleus or the naphthalene nucleus is substituted in o-position to the azo bridge by a OH, NH- or NHR group, wherein R is either lower alkyl, phenyl, lower alkyl-phenyl, chlorophenyl, bromophenyl or ortho-carboxyphenyl.

(2) Disazo dyestuffs which are derived from the dyestufis defined above under (1), wherein one benzene ring bears, in p-position to the azo bridge or in p-position to a metallizable hydroxy substituent defined above, a benzeneazo or naphthalene-azo substituent.

These dyestuffs defined above under 1) and (2) either bear no further substituents, or they are further ring-substituted, preferably in a position other than ortho, to the metallizable azo bridge, namely, alkyl with from 1 to preferably not more than 12 carbon atoms, e.g. methyl, ethyl, propyl, butyl, amyl, hexyl, .octyl, decyl or dodecyl; cycloaliphatic substituents, particularly cyclohexyl; araliphatic substituents, particularly benzyl or phenylethyl; aromatic substituents, especially phenyl, chlorophenyl, brornophenyl, lower alkyl-phenyl, lower alkoxy-phenyl, nitrophenyl; lower alkoxy, e.g. ethoxy or methoxy; cycloalkoxy, particularly cyclohexyloxy; aralkoxy, especially benzyloxy; aryloxy, especially phenoxy or lower alkoxyphenoxy; acylamino substituents, especially alkanoylamino, preferably with a total of from 2 to 7 carbon atoms; halogen substituents such as fluorine, chlorine or bromine; carbamyl or sulfamyl groups wherein the nitrogen atom is mono-substituted with alkyl with 1 to 8 carbon atoms, or phenyl, or cyclohexyl, or wherein the nitrogen atom is di-substituted with two alkyl groups or with one alkyl and one phenyl or one alkyl and one alkyl-phenyl radical, the total number of carbon atoms of the two nitrogen substituents being from 2 to 8; sulfonic acid aryl ester radicals, especially phenoxy sulfonyl, alkyl sulfonyl with from 1 to 6, and preferably from 3 to 6 carbon atoms, phenylsulfonyl, lower alkyl phenylsulfonyl, lower alkoxy carbonyl, lower alkoxy carbonyl amino, alkoxy carbonyl with a total of from 2 to 8 carbon atoms, cyano, trifluoromethyl, amino, hydroxyl and/ or nitro substituents.

The term lower as used herein in connection with an aliphatic group means that the group has from 1 to not more than 4 carbon atoms.

(3) Monoazo dyestuffs of the benzene-azo-pyrazol-S- one and the benzene-azo-(S-amino-pyrazole) series, where in the l-position .of the pyrazole nucleus is substituted with lower alkyl, phenyl, or naphthyl and the 3-position is substituted with lower alkyl or carbamyl, or carbamyl wherein the nitrogen atom is either mono-substituted with alkyl with 1 to 8 carbon atoms or phenyl, or cyclohexyl, or wherein the nitrogen atom is di-substituted with two alkyl groups or with one alkyl and one phenyl or one alkyl and one alkyl-phenyl radical, the total number of carbon atoms of the two nitrogen substituents being from 2 to 8, wherein the benzene ring bears, in o-position to the azo bridge, one of the substituents OH and COOH. The remaining positions of the benzene ring are either unsubstituted or substituted by the ring substituents listed above for (1) and (2).

(4) Disazo dyestuffs derived from the monoazo dyestuffs described under (3), wherein the benzene ring is substituted in p-position to the azo bridge or in p-position to the metallizable OH substituent with phenylazo or naphthylazo.

Again, the benzene or naphthalene nuclei of the dyestuif molecules defined under (3) and (4) are either free from further substituents or contain substituents from the class defined above as permissible ring substituents.

(5) Monoazo dyestuffs of the naphthalene-azo-benzene or the naphthalene-azo-naphthalene series, wherein one naphthalene nucleus bears, in o-position to the azo bridge, a metallizable COOH group, while the other component, either a benzene or a naphthalene ring, bears in position to the azo bridge a -OH, NH or NHR group, wherein R is either lower alkyl, phenyl, lower alkyl-phenyl, chlorophenyl, bromophenyl or ortho-carboxyphenyl.

(6) Monoazo dyestuffs of the naphthalene-azo-pyrazol- -one and the naphthalene-azo-(S-amino-pyrazole) series, wherein the naphthalene nucleus bears, in o-position to the azo bridge, a COOH group. The naphthalene, and especially benzene, nuclei of these dyestuffs where the latter are present in l-position at the pyrazole nucleus are either unsubstituted or substituted with ring substituents of the class defined above; the pyrazole nuclei are substituted in 1- and 3-position as defined under (3).

(7) Azomethine dyestuffs of the benzene-azomethinebenzene and the benzene-azo-benzene-naphthalene series, wherein the benzene nucleus linked to the nitrogen atom of the azomethine bridge bears, in o-position to said bridge, a --OH or COOH group while the nucleus of the other component bears, in o-position to the bridge, a hydroxy group. The nuclei of these dyestuffs are either free from further substituents or bear further ring-substituents of the class defined above.

(8) Azomethine dyestufis derived from the dyestuffs defined in (7) above, wherein either the benzene ring linked to the nitrogen atom of the azomethine bridge bears, in p-position to said bridge or in p-position to a metallizable OH group, or wherein a benzene nucleus linked to the methine group of the azomethine bridge bears, in pposition to the metallizable hydroxy group, a phenylazo or naphthylazo substituent. The aromatic nuclei of these dyestuffs are either free from further substituents or are further substituted with ring-substituents of the class defined above.

(9) Azomethine dyestuffs of the naphthalene-azomethine-benzene or the naphthalene-azomethine-naphthalene series, wherein the naphthalene nucleus linked to the nitrogen atom of the azomethine bridge bears, in o-position to said bridge, a COOH group, while the nucleus of the other component bears, in o-position to said bridge, a .hydroxyl group. The aryl nuclei of these 4 dyestuffs are either unsubstituted or substituted with ring-substituents of the class described above.

Primarily the metallizable groups in the o,o'-positions of azo or azomethine compounds are responsible for the metallization of these dyestuffs, e.g. hydroxyl, carboxyl or amino groups. However, other dyestuffs with a different type of metal complexing configuration which contain an o(lower alkyl carbonyl)phenol hydroxycarboxy-hydroxy-phenyl-o-amino-carboxyphenyl grouping such as the o-acetyl-phenol or salicylic acid radical, can also be used. Of this last-mentioned group of dyestuffs, there are used especially (10) The monoazo dyestufls of the benzene-azo-3- carboxy-4-hydroxy-benzene series and the benzene-azo- 3carboxy-4-amino-benzene series and the disazo dyestuffs of the benzene-azo-benzene-azo-3carboxy-4-hydroxy-benzene series. The benzene nuclei of these dyestuffs are either unsubstituted or substituted with ringsubstituents of the class described above.

substituents of a hydrophobic character, in particular alkyl radicals having 4 to 12 carbon atoms, but also the nitro group and/or halogen substituents, especially chlorine, bromine or fluorine, or trifiuoromethyl, are preferred ring-substituents. When orange, brown, olive, bordeaux or gray shades are to be produced, particularly good results are obtained with the dyestuffs defined above under (1), (2), (3) and (4), the phenyl-azo substituent being preferred in the case of dyestuffs defined under (2) and (4), in which preferred classes of dyestuffs the carbocyclic nuclei are either free from further ringsubstituents or substituted with alkyl having 4 to 12 carbon atoms, fluorine, chlorine, bromine and/or nitro.

When yellow shades are to be obtained, azomethine dyestuffs defined above under (7) and (8) are preferred, in which the aromatic nuclei are either unsubstituted or substituted with alkyl having 4 to 12 carbon atoms, nitro, fluorine, chlorine or bromine.

Dyeing is performed from a weakly alkaline, neutral or weakly acid, preferably aqueous dyebath wherein the dyestuff is finely dispersed as a solution and/or a fine suspension, preferably at boiling temperature, or at a temperature above C. under corresponding excess pressure. Aqueous dispersions used as the dyebath according to the invention preferably contain as dispersing agents condensation products of formaldehyde and naphthalene sulfonic acids, of unsulfonated or sulfonated amines and higher fatty acids, e.g., of p-anisidine sulfonic acid with coconut oil fatty acid in a molar ratio of 1:1 or polyethylene-glycol ether of fatty alcohols with ethylene oxide in a molar ratio of from 1:10 to 1:20. Contact time between the dyebath and the goods to be dyed is preferably about 30 to minutes.

It is particularly surprising that, in this relatively short time, there occurs formation of nickel dyestuff complexes by a metathetic reaction with at least a substantial portion (ca. 5%) to all of the organic nickel chelate dye acceptors initially present in the polyolefine material being dyed.

Printing is performed with a printing paste which contains the usual thickeners, e.g. water-soluble salts of alginic acids or crystal gum solution as well as, optionally, other additives usual in textile printing, such as urea. After printing, the print is fixed by known methods, e.g. by steaming at higher temperatures, preferably not exceeding about C. in the case of polypropylene and not exceeding 115 C. in the case of polyethylene.

The dyeings and prints on polyolefine articles, in particular of polypropylene fibers produced by the process according to the invention, are very strong in color, and they also have good wet and wash fastness including fastness to perspiration, as well as fastuess to light, to rubbing, to sublimation, to migration and to gas fumes.

These outstanding fastness properties are due to the formation, particularly in the surface strata of the polyolefine material, of chelate complexes of the nickel atoms plexes Of the formula wherein A is a dye acceptor radical selected from the group consisting of alkylated diphenyl sulfide nickel chelate, nickel acetylacetonate, Ni-salt of glycine, 8- hydroxy-quinoline nickel complex, o-dihydroxy-benzene nickel complex, o-hydroxy-benzophenone nickel complex, salicylic aldehyde nickel complex radicals, and

B represents the radical of one of the dyestuffs defined above under (1) to (10),

X and X being the residues of two metallizable substituents as defined supra.

All dyestutfs of classes (1) to (10) must be free from -SO H substituents and also from such COOH and the like salt-forming substituents unless the latter are capable of .chelating nickel atoms present in the polyolefine material being dyed.

The following examples illustrate the invention. Where not otherwise stated, parts and percentages are given by weight. The temperatures are in degrees centigrade. The relationship of parts by weight to parts by volume is as that of grams to cubic centimeters.

Example 1 (a) 250 parts of unstabilized polypropylene powder, 0.25 part of 2,2-dihydroxy-3,3-di-tert. butyl-5,5-di-ethyldiphenylmethane and 3.75 parts of the complex nickel compound from 1 atom of nickel and 2 molecules of 2,2-

with 4 parts of the disodium salt of dinaphthylmethane disulfonic acid. The fabric is introduced into the warm bath, the temperature is raised to the boil within 30 minutes and the bath is kept at this temperature for minutes. The fabric is then rinsed hot and cold.

An orange colored fiber is obtained which is fast in particular to light, washing and rubbing.

Example 2 Example 1 is reacted, but 3.75 parts of nickel acetylacetone are used instead of 3.75 parts of the complex nickel compound from 1 atom of nickel and 2 molecules of 2,2-dihydroxy-5,5-di-tert. octyl-diphenyl sulfide; colored fibers are obtained which are also dyed on orange shade with the dyestuff mentioned in Example 1. The dyeings are also fast to light and washing.

Example 3 Example 1 is repeated, but instead of the dyestuff used in the same process, 2 parts of a dyestuff preparation from 3 parts of the monoazo dyestutf of the formula and 4 parts of the disodium salt of dinaphthylmethane disulfonic acid are used; a dark violet-colored fiber is obtained which has good fastness, among others, to light. washing and rubbing.

Example 4 100 parts of yarn produced according to part (a) of Example 1 treated in a dyebath obtained from 5000 parts of Water, 2.5 parts of ammonium sulfate and 2 parts of a dyestuif preparation produced by milling 3 parts of the dyestuff of the formula dihydroxy-5,5'-di-tert. octyl-diphenyl sulfide are mixed together in a dry state, then homogenized on a set of mixing rollers at 180 for 5 to 10 minutes and finally sheeted into a foil of 0.5 mm. thickness.

Strips of 6 x 50 mm. of cuts from this foil and 6 to 8 parts thereof are fed into the cylinder of a melt index tester of the type described in the Tentative Method of Test for Measuring Flow Rates of Thermoplastics by Extrusion Plastometer, ASTM Designation: D1238-57T, issued 1952; revised 1957.

As soon as the temperature of the cylinder has attained 230-250", the polypropylene is extruded and simultaneously wound onto a perforated drum. The monofilament so obtained is stretched at the ratio of from 1:6 to 1:8 by rewinding over a stretching device operating at room temperature.

(b) 100 parts of the fibers produced according to the above instructions are treated in a dyebath consisting of 5000 parts of water, 2.5 parts of sodium N-oleyl-N-methyl-aminoethylsulfonate, 2.5 parts of ammonium sulfate and 2 parts of a dyestuif preparation produced by milling 3 parts of the monoazo dyestufl? of the formula Hus): Q r-r HO-C N OzN OH Example 5 Example 4 is repeated, but instead of the dyestuif used therein, 2 parts of a dyestuff preparation from 3 parts of the monoazo dyestuff of the formula and 4 parts of the disodium salt of dinaphthalmethane disulfonic acid are used; a bordeaux colored fiber which has good fastness particularly to light, washing and rubbing is obtained.

Example 6 A fabric made from the nickel-containing polypropylene fibers produced by the process described in part (a) of Example 1 is dyed with 2 parts of the dyestufr' preparation from 3 parts of the monoazo dyestufl? of the formula and 4 parts of the disodium salt of dinaphthylmethane disulfonic acid, under the conditions and with the other ingredients described in Example 4. An orange colored material which has good fastness especially to light, washing and rubbing is obtained.

Example 7 A fabric made from the nickehcontaining polypropylene fibers produced by the process described is dyed with 2 parts of the dyestuff preparation from 3 parts of the disazo dyestutf of the formula and 4 parts of the disodium salt of dinaph thylmethane disulfonic acid, according to the method described in Example 1, all other ingredients and conditions remaining unchanged. A blueish brown colored material is obtained which has good fastness, among others, to light, washing and rubbing.

Example 8 COOH The goods are entered at 50, the bath is brought to 110 within 30 minutes, the goods are dyed for 30 minutes at this temperature and then rinsed first hot and then cold. A vivid yellow-colored yarn is obtained which has good fastness especially to light, washing and rubbing.

Example 9 Example 8 is repeated, but instead of the dyestuif there mentioned, 2 parts of the dyestufi of the formula H? liIO are used; an orange-colored yarn is obtained which has good fastness to in particular light, washing and rubbing.

Example 10 A fabric made from nickel-containing polypropylene fiber produced as described in paragraph (a) of Example 1, is printed with a printing paste of the following composition: 20 g. of the dyestuff preparation from 8.6 parts 'of the monoazo dyestufi of the formula C 0011 H0 C4He and 11.4 parts of the disodium salt of dinaphthylmethane disulfonic acid,

Urea 40 Water 340 Crystal gum solution, 25% 600 In the printing paste of Example 10, which is repeated with otherwise the same procedure, there are used, instead of the dyestufi given therein, 20 g. of a dyestufi": preparation from 8.6 parts of the monoazo dyestuif of the formula and 11.4 parts of the disodium salt of dinaphthylmethane disulfonic acid; gray prints are obtained on the fabric of nickel-containing polypropylene fibers, which prints are fast especially to light, washing and rubbing.

Example 12 250 parts of low-pressure polyethylene granulate containing 0.25 parts of tert. butyl-p-cresol and 0.75 part of dilauryl thiodipropionate as stabilizers, are thoroughly mixed in a mixing drum with 3.75 pants of finely pulverized nickel acetylacetonate. The granules are then melted in an extruder and a monofilament is extruded at'a temperature of 180 through a die of 1.0 mm. diameter. The monofilament obtained is stretched on a hot apparatus to six times its length.

100 parts of the fiber produced as described above are treated in a dyebath consisting of 5000 parts of water, 2.5 parts of sodium N-oleyl-N-methyl-amino ethylsulfonate, and 2.5 parts of amomnium sulfate and 2 parts of dyestutf preparation produced by milling 3 parts of the monoazo dyestutf of the formula with 4 parts of the disodium salt of dinaphthyl methane disulfonic acid.

The monofilament is entered at 50 into the dyebath, the temperature is raised to within 30 minutes and the bath is kept at this temperature for 60 minutes.

A deep grey-colored monofilament is obtained. The dyeing is fast to light, washing and rubbing.

By using with otherwise the same procedure for the COOH groups, for at least about 30 minutes at a production of the polyethylene monofilament, 3.75 parts temperature ranging from about 100 C. to a temof the complex nickel compound obtained from one atom peratlure not exceeding 115 C. in the case of polyof nickel and 2 molecules of 2,2'-dihydroxy-5,5'-di-tert. ethylene and about 145 C. in the case of polypropyloctyl diphenyl sulfide instead of the 3.75 parts of nickel 5 ene, the molar ratio to the nickel chelate present in acetyl acetonate, there is obtained with the same dyestutf the polyolefine goods being colored not exceeding a filament which is also dyed deep grey, and has similar substantially 1:1. good fastness properties. 3. A process for coloring shaped goods of a polyolefine We claim: material selected from the group consisting of shapable 1. A process for coloring shaped goods of a polyolefine polyethylene and shapable polypropylene, comprising, in material selected from the group consisting of shapable combination: polyethylene and shapable polypropylene, comprising, in a) admixing 'with said polyolefine an organic nickel combination:

(a) admixing with said polyolefine an organic nickel chelate selected from the group consisting of alkylated 0,0'-dihydroxydiphenyl sulfide nickel chelate, nickel chelate selected from the group consisting of alkyl acetylacetonate, Ni-s-alt of glycine, 8-hydroxy quin'oated 0,0'-dihydroxydiphenyl sulfide nickel chelate, line nickel complex, o dihydroxy-benzene nickel comnickel acetylacetonate, Ni-salt of glycine, 8-hydroxyplex, o-hydroxy'benzophenone nickel complex, saliquinoline nickel complex, o-dihydroxy-benzene nickel cylic aldehyde nickel complex and ethylene diamine complex, o-hydroxybenzophenone nickel complex, tetraacetate in an amount corresponding to from salicylic aldehyde nickel complex and ethylene di about 0.1 to 1.2% by weight of nickel in the resultamine tetraacetate in an amount corresponding to ing nickel chelate-containing polyolefine material, from about 0.1 to 1.2% by weight of nickel in the and shaping the polyolefine, and resulting nickel chelate-containing polyolefine ma- (b) tacting the resulting shaped nickel chelate-conterial, and shaping the polyolefine, and taining polyolefine goods with an aqueous dispersion (b) contacting the result-ing shaped nickel chelate-con- 2 of a dyestulf consisting of the monovalent radi al of taining polyolefine goods with an aqueous dispersion a benzene-N=CH-benzene dyestuff wherein the benof an azomethine dyestufi selected from the group Zene nucleus linked to the nitr gen atom of the azoconsisting of a benzene-N=CH-benzene dyestuif methine bridge bears, in o-position to said bridge, a and a -N: H- h h 1 d mff, h r metalliza-ble substituent selected from the group conin the benzene nucleus linked to the nitrogen atom sisting of OH and COOH, and the nucleus of of the azomethine bridge bears, in o-position to said the other dyestuff moiety bears a metallizable OH bridge, a metallizable substituent selected from the group in o-position to said bridge, and wherein the group consisting of OH and COOH, and the latter nucleus bears, in para-position to said metalnucleus of the other dyestutf moiety bears a metalzab e OH group, a substituent selected from the lizable OH group in o-position to said bridge, said group consisting of phenyl-N=N- and naphthylazomethine dyestutf being free from SO H groups N=N-, said dyestuif being free from -SO H groups and non-chelatable -COOH groups, for at least and non-chelata'ble COOH gr p for at least about 30 minutes at a temperature ranging from a ut 30 minutes at a temperature ranging from about 100 C. to a temperature not exceeding 115 about 100 C. to a temperature not exceeding 115 C. in the case of polyethylene and about 145 C. in 40 C. in the case of polyethylene and about 145 C. in

the case of polypropylene, the molar ratio to the nickel chelate present in the polyolefine goods being colored not exceding substantially 1:1.

the case of polypropylene, the molar ratio to the nickel chelate present in the polyolefine goods being colored not exceeding substantially 1:1.

2. A process for coloring shaped goods of a polyole 4. A process for coloring shaped goods of a polyolefine fine material selected from the group consisting of shapmaterial selected from the group consisting of shapable able polyethylene and shapable polypropylene, comprispolyethylene and shapable polypropylene, comprising, in ing, in combination: combination:

(a) admixing with said polyolefine an organic nickel (a) admixing with said polyolefine an organic nickel chelate selected from the group consisting of alkylchelate selected from the group consisting of alkylated ated 0,0'-dihydroxydiphenyl sulfide nickel chelate, 0,0-dihydroxydiphenyl sulfide nickel chelate, nickel nickel acetylacetonate, Ni-salt of glycine, 8 hydroxyacetylacetonate, Ni-salt of glycine, 8-hydroxy-quin'oquinoline nickel complex, o-dihydroxy-benzene nickel line nickel complex, o-dihydroxy-benzene nickel comcomplex, o-hydroxybenzophenone nickel complex, plex, o-hydroxy benzophenone nickel complex, salisalicylic aldehyde nickel complex and ethylene dicylic aldehyde nickel complex and ethylene diamine amine tetraacetate in an amount correspondnlg to tetraacetate in an amount corresponding to from from about 0.1 t 1 y f g 0f nlckel m the about 0.1 to 1.2% by weight of nickel in the resultigr i a l 25m fil ziiin igg gfi igi ggyolefinfi ing nickel chelate-containing polyolefine material,

a 9 hi Ffmtacting I fesultglg EEP nickel 9 (bg o itgt z t i h g il f s ilillig silezfi nickel chelate-c0nil iilt ysifif Solidi; Zf tle 3133331 1 23222 53.? e goods l s aqueous dispersion a monoazo dyestutf selected from the group consistg an azomethme q i whlch is a member selected ing of a benZene N:cH benZene dyestufi, and 3 rom the group consisting of a naphthalene-N=CH- zene-N=CH-naphthalene dyestufi, wherein the benbenzene dyestuff a -N=CH-naphtha- Zane nucleus linked to the nitrogen atoms of the lene dyestufllwherein the naphthalene nucleus linked azomethine bridge bears, in o-position to said bridge, f the ff atom of the azomethine bridge bears, a metallizable OH group, and the nucleus of the o'posltlon to Said bridge, a metallizable COOH other dyestufl moiety bears a metallizable OH p, and the nucleus of the other dyestuff moiety group in o-position to said bridge, and wherein the bears a metallilable E P in 1p0siti0n t0 S benzene ring linked to the nitrogen atom of the azob idge, Said azomethine dyestuif being free from methine bridge bears in one of the positions: para to SO3'H groups and non-chelatable COOH groups, said bridge and para to a metallizable OH group, for at least about 30 minutes at a temperature ranga substituent selected from the group consisting of ing from about C. to a temperature not exceedphenyl-N=N- and naphthyl-N=N-, said dyestult being C. in the case of polyethylene and about ing free from --SO H groups and non-chelatable 7 C. in the case of polypropylene, the molar ratio 1 l 1 2 to the nickel chelate present in the polyolefine goods 3,164,438 1/ 1965 Thomas 8--46 being colored not exceeding substantially 1:1. 3,203,752 8/1965 Mills et -a1 8-75 3,240,552 3/1966 Joyner et a1 8-39 References Cited UNITED T T PAT 4 5 I. TRAVIS BROWN, Acting Primary Examiner.

3,148,936 9/1964 Turbak 8-55 D. LEVY, Assistant Examiner. 

